KR102500346B1 - Manufacturing mathod of high density form of catalysts for carbon nanotubes - Google Patents

Manufacturing mathod of high density form of catalysts for carbon nanotubes Download PDF

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KR102500346B1
KR102500346B1 KR1020210045519A KR20210045519A KR102500346B1 KR 102500346 B1 KR102500346 B1 KR 102500346B1 KR 1020210045519 A KR1020210045519 A KR 1020210045519A KR 20210045519 A KR20210045519 A KR 20210045519A KR 102500346 B1 KR102500346 B1 KR 102500346B1
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박영수
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재단법인 한국탄소산업진흥원
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract

본 발명은 단일벽 탄소나노튜브의 합성에 사용되는 촉매/담지체를 지방산과 혼합하여 그래뉼 형태의 촉매/담지체 집합체를 만드는 방법에 관한 것으로, 더욱 상세하게는 분말형태로 합성된 단일벽 탄소나노튜브 촉매/담지체를 스테아르산 등의 지방산이 녹아있는 에탄올, 에스테르 등의 용매와 섞은 후, 펠렛제조기 등과 같은 그래뉼 또는 펠렛형태로 만들수 있는 장비를 통하여, 그래뉼 형태로 만든 후, 건조하여 그래뉼 형태의 단일벽 탄소나노튜브용 촉매/담지체 집합체를 얻는 것으로, 사용되는 지방산의 양은 촉매/담지체를 만드는 방법에 따라 단일벽 탄소나노튜브용 촉매/담지체의 중량대비 0.1~1배의 양을 사용한다. 또한 목적에 따라 사용되는 지방산에 금속전구체를 부착시켜 사용할 수 있는 방법에 대한 것이다.The present invention relates to a method for preparing a granular catalyst/support assembly by mixing a catalyst/support used in the synthesis of single-walled carbon nanotubes with fatty acid, and more particularly, to a single-walled carbon nanotube synthesized in powder form. After mixing the tube catalyst/carrier with a solvent such as ethanol or ester in which fatty acids such as stearic acid are dissolved, it is made into granules through equipment that can be made into granules or pellets such as a pellet maker, and then dried to form granules. To obtain a single-walled carbon nanotube catalyst / supporter assembly, the amount of fatty acid used is 0.1 to 1 times the weight of the single-walled carbon nanotube catalyst / supporter depending on the method of making the catalyst / supporter. do. In addition, it relates to a method that can be used by attaching a metal precursor to a fatty acid used according to the purpose.

Figure 112021040949902-pat00001
Figure 112021040949902-pat00001

Description

단일벽 탄소나노튜브 합성용 촉매/담지체의 고밀도화 방법 {Manufacturing mathod of high density form of catalysts for carbon nanotubes}High density method of catalyst/support for synthesizing single-walled carbon nanotubes {Manufacturing mathod of high density form of catalysts for carbon nanotubes}

본 발명은 단일벽 탄소나노튜브 제조에 사용되는 촉매/담지체 분말을 탄소나노튜브 합성용 반응기에 원활히 공급하기 위해 촉매/담지체를 고밀도하는 방법에 관한 것으로, 더욱 상세하게는 겉밀도가 낮고 미세한 분말형태의 합성된 촉매/담지체를 반응기에 원활한 공급을 위하여 지방산의 저분자물질을 이용하여 고밀도로 뭉쳐 그래뉼 형태로 제조하는 방법에 관한 것이다. The present invention relates to a method for high-density catalyst/support to smoothly supply the catalyst/support powder used in the production of single-walled carbon nanotubes to a reactor for synthesizing carbon nanotubes, and more particularly, to a method having a low apparent density and fine microstructure. It relates to a method for preparing a synthesized catalyst/support in powder form in the form of granules by aggregating them at a high density using low molecular weight fatty acids for smooth supply to a reactor.

단일벽 탄소나노튜브는 기존의 금속 소재들과 비교하여 보면, 밀도가 낮으면서도, 매우 우수한 전기적 성질과 기계적 성질, 열적 성질을 가지고 있어, 전자방출소재, 투명전극 소재 등에 활용되어 왔으며, 최근 이차전지용 도전재에 사용하기 위해 연구가 진행되고 있다. 그러나, 단일벽 나노튜브의 낮은 밀도 및 수십마이크로의 분말 형태로 인한 처리과정에서의 흩날림으로 인한 인체에 대한 유해성 및 전기 제품의 오작동을 발생할 수 있다.Compared to conventional metal materials, single-walled carbon nanotubes have very good electrical, mechanical, and thermal properties, despite their low density, and have been used for electron emission materials and transparent electrode materials. Research is being conducted to use it as a conductive material. However, due to the low density of the single-walled nanotubes and the powder form of several tens of micrometers, scattering during processing may cause harm to the human body and malfunction of electrical appliances.

일반적으로 단일벽 탄소나노튜브는 촉매 전구체(Ferrocene, Cobaltocene 등)를 합성가스 또는 합성용액과 함께 반응기에 공급하여 합성하는 Floating Catalyst Chemicla Vapor Deposition (FC-CVD) 방법, 또는 Ni, Fe, Co 등의 촉매가 포함된 탄소봉을 밀폐된 공간에서 아크방전하여 합성하는 아크방전법, 촉매를 담지체에 담지하여 수직으로 된 반응기에 의해 위아래로 움직이면서 합성되는 유동층(Fludized Bed Reactor, FBR), 촉매가 담지된 촉매/담지체를 반응기의 수평으로 이동시켜서 합성하는 회전형 합성 반응기 (Rotary CVD, R-CVD) 등이 있다. 그 중에서도 촉매를 담지체에 담지하여 합성하는 유동층 및 회전형 합성 반응기는 미세 분말형태의 촉매/담지체 를 사용하고 있으나, 담지체의 종류에 따라 다르지만, 이송 및 처리 과정 중 미세분말이 흩날려, 작업이 어렵게 하거나, 또는 습기 등의 용액을 일부라도 흡수하면, 이송로 및 반응기 벽에 달라붙어 제대로 공급이 되지 않는 단점을 가지고 있다. In general, single-walled carbon nanotubes are synthesized by supplying catalyst precursors (Ferrocene, Cobaltocene, etc.) to a reactor together with synthesis gas or synthesis solution, or the Floating Catalyst Chemicle Vapor Deposition (FC-CVD) method, or Ni, Fe, Co, etc. An arc discharge method in which carbon rods containing a catalyst are synthesized by arc discharge in an enclosed space, a fluidized bed reactor (FBR) in which a catalyst is supported on a support and moved up and down by a vertical reactor, and a catalyst supported There is a rotary synthesis reactor (Rotary CVD, R-CVD) in which the catalyst/support is synthesized by moving the catalyst/support material horizontally in the reactor. Among them, fluidized bed and rotary synthesis reactors in which catalysts are supported on supports and synthesized use catalysts/supports in the form of fine powders. If the work is difficult or even part of the solution such as moisture is absorbed, it has a disadvantage in that it is not properly supplied by sticking to the transfer path and the reactor wall.

본 발명은 상기한 문제점을 해결하기 위해 고안된 것으로 보관 및 취급이 용이하고, 제조가 간단하고, 제조비용이 저렴한 단일벽 탄소나노튜브용 촉매/담지체 그래뉼 제조 방법을 제공하는 데 있다.The present invention has been devised to solve the above problems, and is to provide a method for preparing catalyst/support granules for single-walled carbon nanotubes, which is easy to store and handle, simple to manufacture, and inexpensive to manufacture.

본 발명은 이미 합성된 분말 형태의 단일벽 탄소나노튜브용 촉매/담지체를 담지체 중량 대비 0.05~1배의 지방산이 녹아있는 담지체 중량 1~5배의 에탄올 용액을 이용하여, 펠렛 형태 또는 기존의 분말 촉매보다 큰 형태의 그래뉼로 제조한 후, 이를 건조기를 통한 건조하는 방식으로 원래의 분말 촉매 부피보다 줄어든, 분말이 뭉친 촉매/담지체 그래뉼 제조 방법을 제공한다. The present invention uses an ethanol solution of 1 to 5 times the weight of the support in which 0.05 to 1 times the weight of the support is dissolved in the already synthesized catalyst / support for single-walled carbon nanotubes in the form of a pellet, or Provided is a method for producing catalyst/support granules in which the powder is agglomerated, which is smaller than the original powder catalyst volume by manufacturing granules larger than the conventional powder catalyst and then drying them through a dryer.

본 발명은 미리 합성된 분말 촉매를 간단히 지방산이 녹아있는 에탄을 용액과 혼합하여 펠렛타이저 등의 그래뉼을 제조할 수 있는 장치를 이용하여 그래뉼 형태로 제조 및 건조 공정을 통해 미세분말의 촉매/담지체가 크기가 커지면서 겉보기 밀도가 증가한 그래뉼 형태의 촉매/담지체로 단일벽탄소나노튜브 합성을 위해 흩날림이 적고, 공기중 물기가 흡착되지 않아 취급 및 보관하기가 쉽다. The present invention is prepared in the form of granules using a device capable of producing granules such as a pelletizer by simply mixing a previously synthesized powder catalyst with a solution of ethane in which fatty acids are dissolved, and fine powder catalyst/support through a drying process It is a catalyst/support in the form of granules whose apparent density increases as the size of the sieve increases. It is easy to handle and store because it has little scattering for the synthesis of single-walled carbon nanotubes and does not adsorb moisture in the air.

도 1은 합성된 단일벽 탄소나노튜브용 촉매/담지체의 분말 사진
도 2는 본 발명에 사용되는 그래뉼 형태의 단일벽 탄소나노튜브용 촉매/담지체 제조 공정도.
도 3는 본 발명에 의해 제조된 단일벽 탄소나노튜브용 촉매/담지체 그래뉼 사진.
도 4는 본 발명에 의해 제조한 단일벽 탄소나노튜브용 그래뉼 형태의 촉매/담지체를 이용하여 합성된 단일벽 탄소나노튜브 SEM 및 TEM 이미지(a)와 비교예에 의해 미세한 분말의 촉매/담지체를 이용하여 합성한 단일벽 탄소나노튜브 SEM 이미지(b).1 is a powder photograph of a synthesized catalyst/support for single-walled carbon nanotubes
Figure 2 is a process diagram for manufacturing a catalyst/support for single-walled carbon nanotubes in the form of granules used in the present invention.
3 is a photograph of catalyst/support granules for single-walled carbon nanotubes prepared according to the present invention.
4 is a SEM and TEM image (a) of single-wall carbon nanotubes synthesized using a granular catalyst/support for single-wall carbon nanotubes prepared according to the present invention and a catalyst/carrier of fine powder by a comparative example SEM image of single-walled carbon nanotubes synthesized using a support (b).

본 발명을 첨부된 도면을 참조하여 상세히 설명하면 다음과 같다.The present invention will be described in detail with reference to the accompanying drawings.

일반적으로 촉매/담지체를 사용하여 단일벽 탄소나노튜브를 합성할 경우에 사용되는 미세한 분말 형태의 촉매가 담지된 촉매/담지체를 제조한다. 촉매 전구체 및 담지체를 용액내에서 혼합 후, pH 등의 조절을 통한 담지체에 촉매가 달라붙게 하고, 이를 필터링 및 건조를 통한 용액 제거 후, 분쇄하여 단일벽 탄소나노튜브를 합성한다. 촉매의 담지법은 설명한 담지법 (Precipitation)외에도 공침법 및 연소법 등의 다양한 방법으로 탄소나노튜브용 촉매를 합성할 수 있다. 도1은 일반적으로 CVD 또는 유동층에 의해 합성된 촉매/담지체의 카메라 사진(a)이다. (a)처럼 미세분말상으로 합성된 단일벽 탄소나노튜브용 촉매/담지체는 사용시 흩날림이 많아, 건강 및 장비의 이상을 가져올 수 있다. 도 2는 본 발명에서 사용한 촉매/담지체 그래뉼을 제조하기 위한 공정을 나타낸 것으로, 도1과 같이 일반적으로 합성된 미세 분말상의 촉매/담지체를 소량의 지방산이 녹아있는 용액과, 예를 들면 촉매/담지체 중량의 0.1~1 배의 지방산이 녹아있는 1에서 5배의 에탄올 용액, 혼합한 후, 단순히 압출기 또는 그래뉼 장치에 넣고 뽑아내면, 그래뉼 형태로 만들어진다. 이를 건조기에 넣고 지방산 녹는 온도 이하에서 사용된 용매를 제거하게 되면, 작은 알갱이 형태의 촉매/담지체 집합체는 지방산에 의해 좀더 밀도가 높고 엉켜있는 형태를 가지게 된다. 미세분말을 그래뉼화하여 제조한 촉매/담지체와 미세분말 촉매/담지체를 이용하여 실시예 및 비교예를 통하여 단일벽탄소나노튜브를 합성하여 비교하였다. 그 결과 제조된 단일벽 탄소나노튜브의 형태에는 큰 변화가 없는 것으로 나타났다. In general, a catalyst/support on which a catalyst in the form of a fine powder, which is used when synthesizing single-walled carbon nanotubes using a catalyst/support, is supported is prepared. After mixing the catalyst precursor and the carrier in a solution, the catalyst is allowed to adhere to the carrier by adjusting the pH, etc., the solution is removed through filtering and drying, and then pulverized to synthesize single-walled carbon nanotubes. As for the supporting method of the catalyst, the catalyst for carbon nanotubes can be synthesized by various methods such as a co-precipitation method and a combustion method in addition to the above-described precipitation method. Figure 1 is a camera photograph (a) of a catalyst/support generally synthesized by CVD or fluidized bed. As shown in (a), the catalyst/support for single-walled carbon nanotubes synthesized in the form of a fine powder is often scattered during use, which may cause health and equipment abnormalities. Figure 2 It shows a process for preparing the catalyst/support granules used in the present invention. As shown in FIG. 1, the generally synthesized fine powder catalyst/support is mixed with a solution in which a small amount of fatty acid is dissolved, 1 to 5 times the ethanol solution in which 0.1 to 1 times the weight of fatty acid is dissolved, and then simply put into an extruder or granule device and extracted to form granules. When this is put in a dryer and the solvent used is removed below the melting temperature of the fatty acid, the catalyst/support aggregate in the form of small particles has a more dense and entangled form due to the fatty acid. Single-walled carbon nanotubes were synthesized and compared through Examples and Comparative Examples using the catalyst/support prepared by granulating fine powder and the fine powder catalyst/support. As a result, it was found that there was no significant change in the shape of the manufactured single-walled carbon nanotubes.

이와 같은 그래뉼 형태의 촉매/담지체 집합체는 사용되는 펠렛제조기의 구멍의 크기에 의해 작게는 수백마이크로에서 크게는 밀리미터 크키로 얻을 수 있다. Such granular catalyst/support aggregates can be obtained in sizes ranging from hundreds of microns to as large as millimeters depending on the size of the hole of the pelletizer used.

도 3은 본 특허에서 제공한 도 2의 방법으로 제조한 촉매/담지체 그래뉼을 제조하여 얻은 카메라이미지이다. 먼저, 담지체 마그네슘 산화물에 나노철입자를 담지하여 제조한 100g의 단일벽탄소나노튜브용 촉매/담지체를 촉매/담지체 중량 대비 0.5 배의 즉 50g 스테아르산이 녹아있는 400g 에탄올 용액과 혼합하여 섞은 후, 3mm의 홀을 가진 고추분쇄기 (펠렛제조기)를 이용하여 촉매/담지체 그래뉼을 제조하였다. 그 후 50도에서 24시간 건조하여 최종저으로 촉매/담지체를 얻었다. 그리고, 이 촉매/담지체 그래뉼을 이용하여 열기상화학증착장치를 이용하여 900도에서 단일벽 탄소나노튜브를 합성하였고, SEM 및 TEM으로 분석한 결과를 도 4(a)에 나타내었다. 3 is a camera image obtained by preparing the catalyst/support granules prepared by the method of FIG. 2 provided in this patent. First, 100 g of a catalyst/support for single-walled carbon nanotubes prepared by supporting nano-iron particles on magnesium oxide is mixed with a 400 g ethanol solution in which 50 g stearic acid is dissolved, 0.5 times the weight of the catalyst/support. Then, catalyst/support granules were prepared using a red pepper grinder (pellet maker) having a hole of 3 mm. After that, it was dried at 50 degrees for 24 hours to obtain a catalyst/support as a final layer. Then, using the catalyst/support granules, single-walled carbon nanotubes were synthesized at 900 degrees using a thermal vapor deposition apparatus, and the results of analysis by SEM and TEM are shown in FIG. 4(a).

실시예에서 사용한 단일벽 탄소나노튜브용 촉매/ 담지체 미세분말(도 1)을 이용하여, 단일벽 탄소나노튜브를 제조하였다. 이 미세분말의 촉매/담지체를 열기상화학증착장치를 이용하여 900도에서 단일벽 탄소나노튜브를 합성하였고, SEM으로 분석한 결과를 도 4(b)에 나타내었다.Single-walled carbon nanotubes were prepared using the catalyst/support fine powder for single-walled carbon nanotubes used in Examples (FIG. 1). Single-walled carbon nanotubes were synthesized at 900 degrees from the catalyst/support of this fine powder using a thermal vapor deposition apparatus, and the results of SEM analysis are shown in FIG. 4(b).

Claims (5)

단일벽 탄소나노튜브용 촉매/담지체를 촉매/담지체 중량대비 0.1~1배의 지방산이 녹아있는 촉매/담지체 중량대비 1~5배의 용액과 혼합한 후, 0.1~5mm 크기의 그래뉼 형태로 촉매/담지체 집합체를 제조하는 방법.The catalyst/support for single-walled carbon nanotubes is mixed with a solution containing 0.1 to 1 times the weight of the catalyst/support and 1 to 5 times the weight of the catalyst/support, in which 0.1 to 1 times the weight of the catalyst/support is dissolved, in the form of granules of 0.1 to 5 mm in size. A method for preparing a catalyst/support assembly. 청구항 1항에서, 지방산이라 함은 미리스트산, 스테아르산, 팔미틱산 등 상온에서 고상으로 존재하는 지방산으로, 이것을 이용하여 그래뉼 형태로 촉매/담지체 집합체를 제조하는 방법.The method of claim 1, wherein the fatty acid is a fatty acid that exists in a solid state at room temperature, such as myristic acid, stearic acid, or palmitic acid, and is used to prepare a catalyst/support assembly in a granular form. 청구항 1항에서, 용액이라 함은 에탄올, 메탄올, 에테르 등으로 상온에서 액체상태로 존재하면서 지방산을 녹일 수 있는 물질을 말하는 것으로, 이것을 이용하여 그래뉼 형태로 촉매/담지체 집합체를 제조하는 방법.In claim 1, the solution refers to a substance capable of dissolving fatty acids while existing in a liquid state at room temperature, such as ethanol, methanol, or ether. 청구항 1항에서,
단일벽 탄소나노튜브용 촉매/담지체라 함은 담지체 대비 촉매 중량비율이 0.01에서 0.20인 것으로, 촉매가 담지체와 혼합되어 있는 것으로, 이것을 이용하여 그래뉼 형태로 촉매/담지체 집합체를 제조하는 방법.In claim 1,
Catalyst/support for single-walled carbon nanotubes means that the weight ratio of the catalyst to the support is 0.01 to 0.20, and the catalyst is mixed with the support. A method for producing a catalyst/support assembly in granule form using this . 삭제delete
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